紫外拉曼光谱结合快速产物分析原位跟踪真实MTO反应历程

Since the establishment of methanol to olefins (MTO) process, the advances on the academic research by pseudo in-situ and ex-situ techniques benefit the design of MTO catalysts, products selectivity control, and ultimately the industrial application of DMTO technology. With the aim of precisely tuning the methanol conversion route and products selectivity, in-situ exploration on MTO mechanism under harsh industry conditions is highly desired. In this project, Operando UV Raman technique, combined with rapid analysis techniques, is applied to trace the actual MTO process. The correlation of the formation and evolution of organic species in the working catalyst captured by UV Raman spectroscopy with the analysis of gas phase effluent via multiple on-line techniques can be taken as an effective strategy to probe the transition of MTO process evolved from induction period, via steady-state stage to deactivation stage. On the detailed analysis of the formation and evolution of the initial hydrocarbons, active intermediates and coking species, we could speculate the mechanism of olefin formation co-catalyzed by active hydrocarbon species and the deactivation process induced by coking deposits. Based on the Raman spectrum library established under the industrial conditions, a rapid response and control strategy could be proposed as a descriptor to monitor the three stages of MTO process. This project will provide theoretical and technical supports for the optimization and upgradation of MTO technique.

自从发现甲醇制烯烃（MTO）过程以来，催化剂的发展和过程的不断优化最终促成了DMTO技术的工业化。大量非原位和准原位的研究为设计MTO催化剂、揭示反应途径、控制产物生成提供了有力保障。为了进一步把握MTO反应历程和实现选择性调控，需要在更为严苛的真实反应条件下从事MTO反应的原位观察。本项目利用紫外拉曼光谱结合快速产物分析在线跟踪真实MTO反应历程。通过催化剂上有机物种生成和演变的原位Raman观测和对气相流出物实时在线分析，把握反应由诱导期到高效稳态期以及失活期的进程；根据其中初始烃类物种、活性烃池物种和积碳物种的生成和演变，推测基于活性烃池物种作为共催化剂的烯烃生成和积碳物种引导的失活过程；构建真实的MTO全反应阶段的Raman谱库，建立Raman光谱信号指示的反应快速响应和性能调控机制。项目的开展将为MTO技术优化与升级提供理论和技术支持。

自从发现甲醇制烯烃（MTO）过程以来，催化剂的发展和过程的不断优化最终促成了DMTO技术的工业化。大量非原位和准原位的研究为设计MTO催化剂、揭示反应途径、控制产物生成提供了有力保障。为了进一步把握MTO反应历程和实现选择性调控，需要在更为严苛的真实反应条件下从事MTO反应的原位观察。本项目利用紫外拉曼光谱结合快速产物分析在线跟踪真实MTO反应历程。通过催化剂上有机物种生成和演变的原位Raman观测和对气相流出物实时在线分析，把握反应由诱导期到高效稳态期以及失活期的进程；根据其中初始烃类物种、活性烃池物种和积碳物种的生成和演变，推测基于活性烃池物种作为共催化剂的烯烃生成和积碳物种引导的失活过程；构建真实的MTO全反应阶段的Raman谱库，建立Raman光谱信号指示的反应快速响应和性能调控机制。项目的开展将为MTO技术优化与升级提供理论和技术支持。